Trivinylphosphine Oxide: Synthesis, Characterization, and Polymerization Reactivity Investigated Using Single-Crystal...

Area of Science:

• Materials Science
• Computational Chemistry
• Polymer Chemistry

Background:

• Organophosphorus compounds are vital industrial chemicals.
• Trivinylphosphine oxide (TVPO) is a promising precursor for flame-retardant additives.
• Understanding TVPO polymerization mechanisms is crucial for its industrial application.

Purpose of the Study:

• To investigate the kinetic and thermodynamic aspects of TVPO nucleophilic addition reactions.
• To elucidate the polymerization mechanisms of TVPO.
• To support theoretical findings with experimental data.

Main Methods:

• Density Functional Theory (DFT) simulations were employed to study reaction pathways.
• An X-ray single-crystal study experimentally validated theoretical computations.
• Implicit solvation models (water) and hybrid models (THF) were used to simulate reactions.

Main Results:

• TVPO is preferentially formed at low temperatures due to thermodynamic favorability.
• Anionic addition polymerization of TVPO and VMB initiates at higher temperatures.
• Simulations identified a pseudo-Michael addition mechanism with a four-membered ring transition state.

Conclusions:

• DFT simulations provide valuable insights into TVPO polymerization kinetics and thermodynamics.
• The study supports the use of TVPO as a flame-retardant precursor.
• The identified reaction mechanism offers a basis for controlling TVPO polymerization for industrial applications.